Treatment of oxidized hydrocarbons



Patented Jan. 8, 1952 2,581,505 OFFICE TREATMENT or OXIDIZED HYDROGARBONS Carl Nazelln'er, New Providence, N. J., assignor to Tide. Water Assoc Bayonne, N. J.,

iated Oil Company,

a corporation of Delaware N Drawing. Application January 10, 1948, Serial No. 1,671

The present invention relates to a method for the treatment of oxidized hydrocarbon mixtures to obtain highly desired and useful oxidized prod} ucts therefrom. Morespecifically, the invention relates to the treatment of certain oxidized hydrocarbon mixtures, as are more fully described.

hereinafter, for preparation 1y useful esterified products.

In the oxidation of hydrocarbons, and particularly in the liquid phase oxidation of predominantly paraflinic hydrocarbons by reaction there: of with oxygen of a free oxygen-containing gas, complex oxidized hydrocarbon mixtures are obtained that comprise a Wide variety of oxidized productathe exact nature of which appears to be primarily dependent upon the particular conditions employed for the oxidation. For instance,

andisolation of high by employing certain conditions for effecting the oxidation, oxidized hydrocarbon mixtures may be obtained that have relatively low saponifi-cation values, e. g., lessthan about 400 mgms. KOH per gram and,-hence, contain a substantial amount of mono-functionalsubstances, e. g., monobasic acids, with a negligible amount, ifany, of crystalline difunctional substances. On the other hand,

by varying the conditions under which the oxidation is effected, oxidized hydrocarbon mixtures may be obtained that have relatively high saponification values, e. g., at least about 400 mgms. of KOI-I per gram. For a suitable method for preparation of such high saponification value oxida tion mixtures by liquid phase reaction between hydrocarbon mixtures and oxygen of a free oxy-.,

gen-containing gas, reference is made to my process, and products thereof, disclosed in U. S. Patent No. 2,486,454, issued November 1, 1949. Such oxidized hydrocarbon mixtures contain, in addition to mono-functional substances, a substantial amount of crystalline difunctional substances, e. g., dibasic acids and substances convertible thereto, the attainment of such relatively high saponification values being effective to convert asubstantial amount of the hydrocarbons to polyfunctional, in preference to, monofunctional substances. Generally speaking, oxidized hydrocarbon' mixtures prepared by liquid phase oxidation of predominantly paraffinic hydrocarbons by recombination with an alcohol;

17 Claims. 01. 260-485) ble from the aforesaid oxidized mixture and substantially devoid of theaforesaid undesired compounds, are highly useful for many purposes, as for example, for plasticizing certain types of synthetic resins, the presence of the aforesaid undesirable constituents in the esterified compounds deleteriously affect the utility and performance of the desired products for many usages as they generally impart acidic and/or incomparability characteristics to the esterified products. Itis highly desirable. therefore, to provide a simple and efficient method for the treatment of certain oxidized hydrocarbon mixtures for preparation and recovery therefrom of esterified compounds that are substantially free of the aforesaid saponifiable compounds present in the portion of the oxidized hydrocarbon mixtures accounting for the difference between the acid and saponification values thereof. Thus, it is a primary object of this invention to provide a simple and efficient method for treatment of oxidized hydrocarbon mixtures to accomplish such desired results. i

Generally speaking, the process of this inven tion comprises subjecting a suitable oxidized hydrocarbon mixture to esterification whereby an esterified mixture is obtained containing saponifiablegroups combined with an alcohol, as well as saponifiable groups not in combination with an alcohol and treating the product of theesterification with a suitable alkali-under controlled conditions effective to preferentially saponify the compoundscontaining saponifiable groups that are not in combination with an alcohol without affecting substantial, if any hydrolysis of compounds containing saponifiable groups that are in By practicing the invention in accordance with the disclosure herein, highly effective separation and recovery of the desired esterified, products, substantially free of the aforesaid undesired compounds, is readily at- ,l. tained.

action thereof with oxygen of a free oxygen-containing gas are characterizedrby having an acid value lower than the saponification value; In

many-instances, the acid to saponification value differential is substantial, as forexample, the acid value may. often represent about 60% of the Inbroad aspect, the oxidized hydrocarbon mixtures contemplated for use as starting materials for practicing this; invention may be defined as oxidized hydrocarbon mixtures that (a) are prepared byliquid phase oxidation of hydrocarbons by reaction thereof with oxygen of a free oxygencontaining gas and (b) are further characterized by'having a difference between the acid and saponification 3 value thereof. In a particularly practical embodiment, the invention is directed saponification value. Such oxidized hydrocarbon;

mixtures-represent a potential source for prepara-,

tion of valuable and highly useful esterified products. .I-lowever, in'the treatment of such oxidized mixtures for preparation and isolation of esterified-products therefrom, I have found that, in mostinstances, the esterified productsobtained contain certain undesired saponifiable compounds thatar'e constituents of the portion of the oxidizedhydrocarbon mixture accounting for the (111-.

to the use of, as starting materials, oxidized hydroc'arbon mixtureshaving the aforesaid characteristics and having a saponification value of more than 400 mgms. of KOI-I per gram as for .example, 500 to 625 and even higher, and, hence,

contain a substantial amount of crystalline dibasic acids and polyfunctional substances convertiblethereto and which oxidized hydrocarbon mixtures are prepared by the process of aforesaid BatentNo. 2,486,454 Spcificillustrations there-- about 60% of the total saponifiable groups.

of are oxidized hydrocarbon mixtures disclosed in the examples set forth hereinafter. As aforesaid, in the treatment of such oxidized hydrocarbon mixtures for preparation and isolation of esterified products, the esterified productsobtained are often found to contain certain undesiredsapOni: fiable compounds that are constituents of the por tion of the oxidized hydrocarbon mixtureaccounting for the difference betweenthe acid and saponification values thereof. For example, by subjecting such oxidized hydrocarbon mixtures to esterification with an excess of a suitable alcohol under certainconventional esterification conditions, and treating the esterified mixture forrecovery of desiredesterified products, as for example, by distillation, the distillate fractions are found to have an acid value higher than the acid value of the esterified mixture charged to the distillation. Such results are obtained when all of 1 the ,saponifiable groups in the oxidized hydrocarbon mixture are not in combination with an alcohol after subjecting such a mixture to esterification, and hence, the esterified mixture contains both saponifiable groups that are-in com-' mixtures totreatment with a suitable alkali under controlled conditions, as is more fully described hereinafter, the desired esterified products are obtainable ina form substantially free of the aforesaid undesirable constituents.

With further reference to theoxidized hydro-i carbon mixtures suitable for use as starting materials for practicing this invention, I have found that, upon subjecting such mixtures to esterification" with an excess of a suitable alcohohusing certain conventional esterification methods, the amount of alcohol that reacts is often considerably less than the theoretical required for reaction with all of the saponifiable groups in the mixtures. In many instances, the amount of alcohol that reacts is found to be substantially equivalent to the free acid value of the mixture, which, as aforesaid, may generally represent only Although the oxidized hydrocarbon mixtures, prior to subjection thereof to esterification with an excess of a suitable alcohol, may contain, as components of the portionaccounting for thedifference between acid and saponification value therei of, compounds whose saponifiable groups are already combined with an alcohol, and hence, such compounds do not react with the alcohol used in the aforesaid esterification, inmost instances, the

' portion of the oxidized hydrocarbon mixture that accounts for the difference between the acid and saponification value is comprised predominately, or wholly, of compounds having saponiflable groups that are not combined with an alcohol,

the primary objectof. this inventionzis toisolate 4 from'esterified oxidized hydrocarbon mixtures. having the aforesaid characteristics, compounds having saponifiable groups combined with an alcohol that are substantially free of compounds containing saponifiable groups that are not combined with an alcohol prior to subjection of the oxidized hydrocarbon mixture to esterification with an alcohol and which groups are not combined with-an alcohol as a result of having subtheesterified mixture that contain saponifiable groups not combined with an alcohol without thean alcohol.

jectedthe oxidized hydrocarbon mixture to esterification. v

In accordance with this invention, esterified mixtures as aforesaid that contain saponiflable groups combined-withan alcohol and-saponifiable groups not'in combination with an alcohol, are

treated with a'suitable alkali under controlled" conditions to selectively saponify constituents of occurrence-of substantial, if any, hydrolysis of the. desired esterified products, i. e., products whose saponifiabl'egroups are in combination with In broad aspect, the aforesaid selective treatment comprises adding tothe esterified mixture a suitable alkaliin an amount at least equivalent to the'numberof saponifiable groups present therein that are not in combination with an alcohol. In order thatselectiveisolation of the desired esterifiedproducts may be effected, it is important that thealkali addition. be made in a controlled manner so that, during addition of the alkali and until an-amount has been added- 7 equivalent to the number of saponifiable groups not in combination'with an alcohol, liberation of alcohol does not occur, if at all,in other than a negligible amount, as-liberation of alcohol before the aforesaid amount of alkali addition has been completed evidences that undesired hydrolysis of gthe desired esterified product .is being effected simultaneously with saponification of the undesired constituents. Occurrence of such hydrolysis :is undesirable in that it results in de-' creasedyields of the desired products.

trolled additionof alkali as aforesaid, an alkali treated esterified mixture is obtained from which the desired esterified products are recoverablesubstantially free of the compounds containing saponifiable groups that were-not combined with an alcohol. tionresides .inthe-discovery that by the controlled alkalitreatment of the esterified mixtures, selectives separation is effected between the desired esterified products.and compounds having saponifiable groups that are not combined with an alcohol. "As aforesaid, in practicing the invention, theaalkali' additionis made in acontrolled manner so that, until an amount of alkali'is added-equivalent to the number of saponifiable groups in the esterified mixture that are not combined with an alcohol, the concentration of alkali present:- inthe'mixture is maintained at below the amount effective to liberate anysubstantial, if any,

amount of alcohol, the occurrence of which-evi dences that desired'esterified products are undergoing hydrolysis.

eral. methods that may suitably :be employed are described hereinafter. Forinstance, one method thatmay be suitablyemployed is toigradually add thealkali, either continuously or intermittently, totheiesterified mixture .until an amount of alkali An important feature of this inven- Although the invention is not to be consideredlirnited to anyparticular'method' for-controlling the addition of the alkali to the esterified: mixture so as .to provide the resultsembodied herein, for purposes of illustration, sev-- gradually adding the alkali to the esterified mix-- turewhile observing the time required for disappearance of indicator color. The alkali addition is continued in this manner until the time required for disappearance of indicator color increases materially, the rate and/or amount of the alkali addition being controlled so as to prevent liberation of alcohol prior to the time required for disappearance of indicator color to increase materially. When practicedin this manner, the persistence of indicator color evidences that substantially complete saponiflcation of the undesired, compounds has been effected without the occurrence of anysubstantial, if any, hydrolysis of thedesired esterified products. When the time required for disappearance of indicator color has materially increased, the alkali addition is discontinued,- as otherwise, hydrolysis of the desired esterified products would begin to occur, resulting in decreased yield thereof. In some instances, itl'may be desired to sacrifice yields of the desired products in favor of insuring that the undesired substances are fully saponified, and, hence, for such a-purp'ose, the alkali may be added in an amount slightly in excess of that required to reach the indicator end point, i. e., slightly in excess of the theoretical equivalents for the number of saponifiable groupsinthe esterified mixture that were not in combination with an alcohol. Although the aforesaid methods represent highly practical embodiments for practicing the invention, it is within the scope of the present invention to embody other methods for determining the desired rate of alkali addition as long as the addition is made in a controlled manner effective to selectively saponify the aforesaid undesired groups without substanti l if any, liberation of alcohol in the esterified mixture until an amount of alkali is added at least equivalent to the number of saponifiable groups in the mixture that were not in combination with an alcohol.

While the present inventiomas is more fully described hereinafter, isldescribed by use of the 5 ,hydroxidesof sodium and potassium for the selective treatment of the aforesaid esterified oxidized.

hydrocarbon mixtures, such alkalies have been employed for purposes of illustration without intending that the scope of this invention be limited thereto. In preferred embodiment, however,

the alkalies employed comprise the hydroxides of the alkaline earth and alkali metals, suitable examples of which include the hydroxides of sodium,

potassium; calciumand the like. The alkalies are. -preferablyemployed in aqueous solutions, or in solution with a solvent that is substantially immiscible with esters. and more specifically, is not miscible with the desired esterified products obtained by subjecting esterified oxidized hydrocar- .bon mixtures as aforesaidto the selective alkali treatment of this invention. Illustrations of such solutions include aqueous solutions of the alkali and alkaline earth metals, solutions thereof in certain alcohols, as for example, glycol, and the la rilken The following examples are set forth to illustrate specific embodiments of the invention without intending that the invention be limited thereto:

EXAMPLE I tion with air until the mixture had an acid value of 329 and a saponification value of 560 mgms. of KOH per gram. The mixture was subjected to esterification using butyl alcohol inan'amount 10% in excess of the theoretical amount required to react with the saponifiable groups in the mixture. The esterification was carried out by re- 0 oxidized hydrocarbon mixture. The esterified mixture had an acid value of less than 0.2 milliequivalent per gram.

The aforesaid esterified mixture was vacuum distilled under conditions set forth in thefollow- 'ing tabulation, the distillate being collected in fractions as shown:

Table I I w ift r eig c Saponifica- Cut 0 Cut based on Distillation Pressure, gfigf tion Value of gflg gf ggr 532 51 5 Range 0 Hg meqs./gm. ggf of Out of Cut Mixture 1 5 50-110 6 0. 2 6. 8 147 165 ii iifii 3'3 3'5 33 1 13 143-157 4 O. 3 7. 7 280 I? lititi i s: a 41 1so-244 2 119 7:6 32 III: 13 244-2eo 5 2,; l 7.4 its Mega/gm.=milliequivalents/gram (ml. of NKOH per gram). f

1 After extraction of compounds (26%) containing saponiflable groups not in combination with an alcohol, by the alkali treatment of this invention. r a After extraction of water-soluble material (7% of cut).

4 Total overhead. I Residue. i Total recovery.

- An oxidized hydrocarbon mixture was prepared by subjecting paraffin wax to liquid phase reacoht ainedz.

llhe fioregoingadata; the esterifiem-mixture to fractional: distillation; suchjasz conventionally; employed for; isolation of esterified; products. each: ofz-theadistillate fractions:

hadea-m acidt-valueihigherj than the: esterified. mix- .AS; shown," whereas-the chargalmaterialu had. an acid: value:

turea charged. tothe. 'distillatiom shows .;-thatby. subjecting;

lowenithan-Oelmegs/g thedower fractions (cuts higheriractionsiicuts 4A0); consisting predomi- V nantlyiotdifunctionalsubstances; had acid values ranging from:0.3=2.4; y. .Itliszclear, therefore, that l-SJz; consisting predominantlyof'monofunctional i substancesh hadan .acid value.1. of;. 0.2. and the.

not .only :isdistillation.inefiective; to provide esterifield'..-.products' substantially freei 0f: undesiredcompounds; i. e.',' the. compounds imparting acidic values; but. is further undesirable in that a it' re sulted; in: conversion;- of: substantially acidic-free compoundsinthe esterifiedmixture to-compounds:

haying; freeacid groups;

10.1mm). 10.: having; a distillation: range. of 244.

to;26.0'.9iC.; acid value of 2.4.meqs./gm. and sapon ificationofi 7.4.meqs/gmiwaswashed with water and; then with. aqueousasodium; bicarbonate in accordance with conventional procedures for re-I- moval.Zof wateresoluble' and iacidic substances. but the? .rafiinate was 1. found to. contain compounds having; saponifiablec groups. that were not .combined with an alcohol. In accordance with this invention, the rafiinateawascrefluxed with aqueous acetone whileaqueous.KQH was 1 added; radually, i. .e.,;drop vise, :to; the railinatey inthe presence of thymolphthalein,.. until. a. pronounced increase occurred i the; timerequired: fordisappearance of. indica lq -cplor up towhich timeno ascertainable-.lileeratioryof alcohol occurred. The alkali additionlwas continued until, after addition of each drop of indicator color, the; time of color; pen istence.;increas e d; from rapid disappearance to; about. 10 minutes. 1 Whenthetime required'for disappearance of indicator colorhadv thus inall) creased materiallyithe alkali addition was, discontinued. The, alkali treated mixture had separatedintortwo layers; the top layer wasremoved and-,, uponrqanalysisgave the following values evidencing. that byusezof the aioredescribed con-r. trolled-alkaliadditionrtreatment, efiective isola- 1 tion of substantially pure dibutyl esters of: diF' acids: ave-raging about 15 carbon, atoms had been Purified Cut 10 decanedioate Experimental values Theoretical values EsterValue (meqsilgm-Juunl 53; 5. 2. Equiva1entW'elght l89 .e 191. MolecularWeight; about 400 (cem- 382 phor freezing point).

The bottom layer was distilledfto remove watert and upon heating of the driedproduct with an excess of alkali, butyl alcohol liberation did not;

occur, thusevidencing that the aforesaid selective alkali treatmentof the distillates (cut 10) had removed compounds whose saponifiable groups were not combined with an alcohol.

7 XAMPLE II Cut No. 4 (see Table I in Example I) having an acid value of 0.3 me /gm. and a saponification value of 7.7' meqs/gm. was treated by addition thereto of aqueous KOH while refluxing the out with an equal volume of water. The alkali was Dibutyl Pentaaddede dropwise;.:. ini'zlthe. prese'm'ie.- of thymola phthalein sudden: increase, (from aboutBd seconds toraboutlOminutes) occurred inthe time required. for disappearance: of indicator color after each s 1 increment of, the alkalL addition.

Tota-li alkali additionewas.substantially;equivalent. toi-ionenthirdiof the: sa-ponifiable: value: of the-cut; V and; duringadditiomithereof,. no substantiaLi if" anymlcohol liberationhad occurred. Upon;com,--..

pletiomoi: thdal-kali. addition, the alkali-.: treated material: had; formed-rtwo; :layers, :the; top; layer (%.:ofitthe; cut) vwas; ren'l'oved and distilled to yields a: butyl. esteriofz: 1A0 equivalent weight and...

aboilhfifiildirolieculan weight; i. e. ,1 a .dibutyl ester; of

fAnf'oxidi'zed hydrocarbon m'ikture (1420 g.),

prepared byair biowing'of Fi' meltin g point paraifin wax at l-20-' inthe presence of of manganese "naphthenate; and having an acid" value-ch62, meqsr/gm and a saponiflcation value of 1013: meqs/ m: was subjected to; esterification:

by refiuxingwvithranexcess .of butan'ol at' 113"- 122 -The esterifi'cationwas carried onfor 30 hours. -E cess butanol' -"was distilledi Off, and the" residue-.1 reaction mixture analyzed to a saponi fidation-value of'ld Apo'r'tion (20 g fofflthe, residual reaction mix- 'tur wva's analyzed forbutyl'content by adding an'excess" of KOH; anddistilling thethus treated substanceto remove: butanol liberated by saponimanta-with KOHi The amount of butanol relcoveredavas. i513 gramszf'liheoretically, ifall of the 1 saponifi'able' groups of the residual mixture' werecombi'nedwith. butanol; the amount. of butanol liberated by the alkali wouldf be 10.8 grams: However-, theliberationof'only 58% of 1 thetheoreticaIamount of: butanol" evidences that of'theytotal saponifiable groups in the residual mixture, "only 'ab'out 58%-thereof were combined with b itanol.

' esters conde'nsed in an ice -trap. Thepurpose' of the fi'a'sh= distillationwas to r'er'nov'e a small amountof polymer-1emana es bottoms to decrease the possibility of undesirable emulsification during the alkali treatment and layer separation as described hereinafter.

Upon analysis. the flash distillate was found to have a butyl'conte'ntof 62.5% based on saponifi'cationc value thereof. In accordance with this invention, the distillate was treated by adding thereto an amount'cf aqueous KOH equivalent to 37.5% of the saponifiable groups in the disv tillate The required amount of alkali, dissolved in four times its weightof water, was added in small portions over a period of one hour while Themain batchofthe' oxidized hydrocarbon rethatavastreatedwith butanol' under the V aioresaid esterification procedure was flash distilldfat 350 and'f ZiZE'mm'Jpressure and yielded and a bottom layer containing the alkali salts of compounds in the esterified mixture that contained saponifiable groups not in combination with an alcohol. The top layer was vacuum distilled to provide an overhead fraction (63% of charge to distillation) having a boiling point of 65-l98 C. at 0.6 mm. pressure and a liquid bottoms product (37% of the charge). The overhead fraction was analyzed for butyl content by heating thereof with an excess of diethylene glycol at 200 C. with a trace of sodium as exchange catalyst until no more butanol distilled off through a Widmer column and an amount of butanol was recovered equal to 96% of the theoretical value based on the saponifiable groups in the aforesaid overhead fraction. The aforesaid liquid bottoms was treated in a similar manner, and the amount of butanol recovered equalled 93% of the theoretical value based on the saponification value of the bottoms product. In view of such high butanol recoveries from both fractions of the top layer, obtained from the aforesaid controlled alkali treatment of the esterified oxidized hydrocarbon mixture, it is evident that the top layer was substantially all comprised of butyl esters that were substantially free of compounds in the esterified mixture containing saponiflable groups that were not combined with an alcohol.

The bottom layer, obtained from the controlled alkali treatment of the aforesaid esterified mix' ture, was concentrated by evaporation, and concentrated HCl added thereto in' an amount equivalent to the amount of alkali used in the aforesaid controlled alkali treatment, i. e., 37.5% of the total saponifiable groups inthe esterified mixture- The material liberated by the I-IClwas extracted with methyl ethyl ketone, distilled to recover methyl ethyl ketone, andrefiuxed with an excess of z-ethyl hexanol until water evolution ceased. The crude esterified-product obtained was vacuum distilled, and the distillate treated at 95 (3., while being agitated by stirring, 5

by gradually adding thereto aqueous KOH until the time required for indicator color disappearance increased materially. The total amount of alkali added was equivalent to 24% of the saponifiable equivalents. The alkali treatedmaterial separated into two layers. The top layer wasdistilled; a small forerun representing less than 5% of the total 2-ethyl hexanol equivalents was obtained showing that only minute quantities of the desired esterified products were hydrolyzed. The main cut of distilled 2-ethyl hexyl esters had an acid value of 0.06 and a saponification value of 5.0 meqs./gm., and, upon saponification with alkali, liberated 90% of the theoretical 2-ethyl hexanol. i

EXAMPLE IV In a manner similar to that set forth in Example III, a crude esterified mixture was prepared by subjecting the oxidized hydrocarbon mixture to esterification with an excess of buwas equal to 54% ofthe theoretical equivalents based on the saponification value of the aforesaid esterified mixture.

In accordance with this invention, the aforesaid exchange reaction mixture while refluxing at C. was treated by gradual addition thereto of aqueous KOH in the presence of thymolphthalein as an indicator. The alkali was added over a period of 2 /2 hours in twenty portions, the addition being discontinued when the time of disappearance of indicator color increased from about 2 to 14 minutes. During the alkali addition, there was no ascertainable liberation of alcohol. The alkali treated mixture had formed into 2 layers. Thetop layer was separated, and distilled to provide a forerun of less than 3% by weight (about 4% of the total possible) of 2-ethylhexanol, illustrating that relatively negligible attack had occurred of esterified products whose saponifiable groups were combined with an alcohol. The distilled esterified product analyzed to give a saponification value of 5.3 meqs;/g. and a negligible acid value of 0.05, showing that upon distillation of esters purified by the alkali treatment of this invention no decomposition to free acids occurred whereas, ifthe esterified oxidized hydrocarbon mixture is subjected to distillation before and without use of the aforesaid alkali treatment, the distillate obtained therefrom has an acid value greater than the esterified oxidized hydrocarbon mixture charged to the distillation.

EXAMPLE V One kilogram of an oxidized hydrocarbon mixture, prepared by liquid phase oxidation of scale wax with air, having an acid value of 5.8 and saponification value of 10 meqs./g. was subjected to esterification in an autoclave with 400 grams of methanol, by gradually heating to 173", C. with shaking at a pressure of 500 lbs/sq. inch. Excess methanol and 'water of reaction were distilled off and the residual product treated with dry'methanol under the aforesaid conditions. The, product obtained was topped to remove excess methanol and water and subjected to continuous flash distillation at 350 C. and 9 mm; pressure. ,Polymeric bottoms amounted to 8%. The overhead was treated at 30 C. with stirring by gradual addition of aqueous sodium hydroxide over a, 2 hour period, until an amount of alkali equivalent to 10% of the total saponification equivalents had been added. The alkali treated mixture separated into two layers. The top layer was removed, and vacuum distilled wherefrom a methyl ester raflinate fraction boiling from 60-187 C. at 8 mm. pressure was obtained having an acid value of 0.08' meq./g., a saponification value 8.3 meqs./g. and a molecular weight of 199.

Oxidized hydrocarbon mixtures,' such as disclosed herein as suitable starting materials for practicing this invention, are complex mixtures of oxidized compounds, the exact structure of which are not known and are not readily determina'ble. For example, 'various theories have been proposed by the prior art as to the possible structure of the compounds accountin for the difference between the acid and saponification values of the oxidized hydrocarbon mixtures. Among these, esters, estolides, lactones, lactone acids, lactides and other esters of alpha-hydroxy acids have been most often mentioned. From such teachings, it was not foreseeable thatthe process of the present invention would perform the function as disclosed, but on the contrary, it weiild be expected that quite the reverse would "1'5. take. place. For, example,, in -the investigational work leading up to the discovery of thepresent invention esters of, alpha hydroxy acidswere preparediorcomparison studies, and it was found --,that-such1 esters hydrolyzed with-ease under the saponifiable. groups thatare not combinable with V .hydrolyzable.esters were present inanyappreciable,quantities, theylwould give rise toequivalent quantities .of ;-a1coho l,-e. g., butanol, during the ,alkali treatment. of this invention. That-such compounds are .apparentlynot present in, anyap- 'pneciable quantities-if any,.appears evidenced by etheiillustrationsof. this invention, as. set forth hereinbefore, showingthe lack of substantial, if ..any, ..alcoholliberation during the controlled. alkali treatment. .,Moreover, if lactone .acids .were present, such. compounds would ,be expected t sterify yieldinglactone esters i which. would hydrolyze, yielding .alkalisoaps. upon.E controlled vsapcmiiilcation in, accordance with, the, method, of

an-ralcohol under theesterification conditions, andadding an alkali tottheaforesaid esterified mixture in an amount at least-substantially 7 equivalent to the'numberofsaponifiable groups -,-in-said esterified mixture that. are not combined --.with-an;alcoholi'but substantially less than an amountof alkaliequivalent to the total number of saponifiable groups in said esterified mixture to selectively 'saponify the compounds: in :said esterifiedmixture that possess saponifiable groupsthat were not combined with analc'ohol,

. said alkali': addition-being made in a controlled this invention, andsuch half-esters would yield analcoholupon boilingwith excess alkali. However, investigation; has. shown that such results are not obtained. Although it..isnot intended that, the ,present-. invention.be limitedby any theories as to the exactstructure of compounds present in the portion'of such mixtures accounting for the differencebetween the acid and saponification Value thereof, it is apparent from theaforesaid description of the invention that by practice thereof, highly efiective preparation; and isolationis realized of esterified compounds that ;.are.sub stantially free of compoundshaving-sa- .ponifiable groups that are-not combined with an alcohol. tive isolation otthedesiredproducts by thenovel treatment disclosed herein is clearlyanunobviousand unexpected resultrepresenting a marked improvement in the art. 7 I Although the present invention has been describedin conjunction with certain preferred embodiments thereof, those skilled in the :art will. readily: recognize that variation and modifications can be made. Such modifications-and variations are .to be considered tobe within the purview: ,of the specification and .scope of the appended claims.

I. claim: V 1. A method for-treatment of an oxidized hydrocarbon mixture-as defined hereinafter to-prepare and facilitate 'recoverability' of desired esterification products thereof, said-oxidized hydrocarbon mixturebeing characterized byha-vi-ng been prepared Zby liquid. phase reaction .of -a"-'hy'- --drocarbon mixture withoxygen of a free oxygencontaining gas, having a substantial difierence between acid-and saponification value, and'further characterized'by containing, as components of" the portion accounting for the 'differencebe- V tween acid and saponiflcationvalue, compounds containing saponifiable groups that are not readilyv combinablewith an alcohol upon treatment of said (oxidized hydrocarbon mixture with analcohol under esterifying conditions, which comprises reacting. jsaid oxidized, hydrocarbon mixture with .an alcohol under esterifying coniditionsto provide an esterified mixture'containing. a. substantial'portion of saponifiable com- The obtainment of such highly efiec- A has been added, the alkali in the esterified mixture is maintained at a concentration less than 'suflicient to 'liberatea substantial amount of 'al- *coholirom said esterified mixture. r V

2,. A method, asdefined in claim 1, wherein the compounds whose "saponifiable groups *are in combination with anjalcohol are-separated from the alkali-treated mixture substantially devoid of admixture with the'selectively saponified compounds that possessed saponifiable groups that werenot'combinable with the alcohol npontreatment-of the oxidized hydrocarbon mixture under I th esterification conditions. i f 3.'method, as-defined in claim 1, wherein the alkali is in solutionwith a liquid that is substantially immiscible with the compounds in the "esterified mixture whose saponifiable groups are 7 combined-withan alcohol,

I 4. Amthomas defined in claim'l, wherein the ment ofthe oxidized hydrocarbon mixture under "theesterificationconditions.

6. A method, asdefined in claim 1, wherein the oxidized hydrocarbonmixture has a saponifica- 'tion-valueof' at least-400.

' 7. A'iniethodQas defined'in claim 6, wherein the --alka'li-'i's i-naqueous solution. 8. A method, as defined in claim 1, whereinthe alkali-treated mixture comprises a layer containing saponifiable compounds whose saponifiable groups are combined with an alcohol substantially devoidof admixture with compounds .possessing -saponifiable groups that were not combined with the alcohol upon treatment of the oxidized hydrocarbon mixture under est erificationconditions andalayer containing the selectively saponified compounds having saponifiable groups that were not combined :with the alcohol r upon treatment-of the {oxidized hydrovcarbon-mixtureaunoler the esterification conditions. r

:9. Awmethod for treatment of anuesterified :oxidizedrhydrocarbon mixture as defined ;hereinafteruto improve the recoverability-of desired ,esterified products thereof, said esterifiedoxidized... hydrocarbon 1 mixture being characterized by containin a substantial-amount-gof saponifiable ;1compounds whose saponifiable groups are .combined with an .alcohol inadmixture "with a saponifiable compounds that are not readily i combinableq-withan alcohol under esterification by liquid phase oxidation of hydrocarbons with oxygen of a free oxygen-containing gas, having a substantial difference between acid and saponification value and containing, as components of the portion accounting for the difference between acid and saponification value, compounds containing saponifiable groups that are not readily combinable with an alcohol upon treatment of said oxidized hydrocarbon mixture under esterifieation conditions, which comprises selectively saponifying the compounds in said esterified mixture that are not in combination with an alcohol by addition to said esterified oxidized hydrocarbon mixture of an alkali in an amount at least substantially equivalent to the number of saponifiable groups in said esterified mixture that are not in combination with an alcohol but substantially less than an amount of alkali equivalent to the total number of saponifiable groups in said esterified mixture, said alkali addition being made in a controlled manner whereby, until an amount of alkali substantially equivalent to the number of saponifiable groups that are not combined with an alcohol has been added, the alkali in the esterified mixture is maintained at a concentration less than suflicient to liberate a substantial amount of alcohol from said esterified mixture.

10. A method, as defined in claim 9, wherein the alkali is in aqueous solution.

11. A method, as defined in claim 9, wherein the oxidized hydrocarbon mixture has a saponification value of at least 400.

12. A method, as defined in claim 9, wherein the alkali is in aqueous solution, the oxidized hydrocarbon has a saponification value of at least 400, and the alkali-treated esterified oxidized hydrocarbon mixture comprises a layer containing saponifiable compounds whose saponifiable groups are combined with an alcohol substantially devoid of admixture with compounds possessing saponifiable groups that were not combinable with an alcohol upon treatment of the oxidized hydrocarbon mixture under esterification conditions and a layer containing the selectively saponified compounds having. saponifiable groups that were not combined with an alcohol upon treatment of the oxidized hydrocarbon mixture under esterification conditions.

13. A method, as defined in claim 9, wherein the layer containing saponifiable compounds whose saponifiable groups are combined with an alcohol is separated from the alkali treated mixture.

14. A method for treatment of an esterified oxidized hydrocarbon mixture as defined hereinafter to improve the recoverability of desired esterified products thereof, said esterified oxidized hydrocarbon mixture being characterized by containing a substantial amount of saponifiable compounds whose saponifiable groups are combined with an alcohol in admixture with saponifiable compounds that are not combined with an alcohol, said esterified oxidized hydrocarbon mixture having been prepared by reacting with an aliphatic alcohol under esterification reaction conditions an oxidized hydrocarbon mixture prepared by liquid phase oxidation of a predominantly aliphatic hydrocarbon mixture with oxygen of a free oxygen containing gas, having a saponification value of at least about 400" "and" a substantial difier'e'n'ce between acid and saponification value, and containing, as components of the portion accounting for the difference between acid andsaponification value, compounds containing saponifiable groups that are; not readily combinable with-an alcohol upon treatment of said oxidized hydrocarbon mixture under esterification conditions, which comprises selectively saponifying the compounds in said esterified mixture that are not in combination with an alcohol by addition to said esterified oxidized hydrocarbon mixture of an aqueous solution of an alkali in an amount at least substantially equivalent to the number of saponifiable groups in said esterified mixture that are not in combination with an alcohol but substantially less than an amount of alkali equivalent to the total number of saponifiable groups in said esterified mixture, said alkali addition being made in a controlled manner whereby, until an amount of alkali substantially equivalent to the number of saponifiable groups that are not combined with an alcohol has been added, the alkali in the esterified mixture is maintained at a concentration less than sufllcient to liberate a substantial amount of alcohol from said esterified mixture.

15. A method, as defined in claim 14, wherein the alkali is an aqueous solution of a hydroxide of a metal from the group consisting of alkali metals and alkaline earth metals.

'16. A method, as defined in claim 15, wherein the esterifying alcohol is an aliphatic monohydric alcohol.

1'7. A method for treatment of an esterified oxidized hydrocarbon mixture as defined hereinafter to improve the recoverability of desired esterified products thereof, said esterified oxidized hydrocarbon mixture being characterized by containing a substantial amount of saponifiable compounds whose saponifiable groups are combined with an alcohol in admixture with saponifiable compounds that are not combined with an alcohol, said esterified oxidized hydrocarbon mixture having been prepared by reacting with an aliphatic alcohol under esterification reaction conditions and oxidized hydrocarbon mixture prepared by liquid phase oxidation of a predominantly aliphatic hydrocarbon mixture with oxygen of a free oxygen-containing gas, having a substantial difference between acid and saponification value, and containing, as components of the portion accounting for the difference between acid and saponification value, compounds containing saponifiable groups that are not readily combinable with an alcohol under esterification conditions, which comprises selectively saponifying compounds in said esterified mixture that are not in combination with an alcohol by addition to said esterified oxidized hydrocarbon mixture of an alkali in an amount at least equivalent to a substantial portion of the saponifiable groups in said esterified mixture that are not in combination with an alcohol but substantially less than an amount of alkali equivalent to the total number of saponifiable groups in said esterified mixture, said alkali addition being made in a controlled manner whereby, upon addition of alkali in an amount up to that substantially equivalent to the saponifiable groups not combined with an alcohol, the alkali in the esterified mixture is maintained at a concentration less than sufficient to liberate a.

r '16 V ,substantial. -"amountr.0f. alcohol: from ;.said'.es,te17i- UNITED STATES. PATENTS fled: mix ure- Number "Name Date I T 2,054,979 'Jahrstorfer Sept. 22, 1936 "REFERENCES CITED 5 2,153,302 -Ew1ng Apr. 4, 195139 me: of. thiszpatent: 

1. A METHOD FOR TREATMENT OF AN OXIDIZED HYDROCARBON MIXTURE AS DEFINED HEREINAFTER TO PREPARE AND FACILITATE RECOVERABILITY OF DESIRED ESTERIFICATION PRODUCTS THEREOF. SAID OXIDIZED HYDROCARBON MIXTURE BEING CHARACTERIZED BY HAVING BEEN PREPARED BY LIQUID PHASE REACTION OF A HYDROCARBON MIXTURE WITH OXYGEN OF A FREE OXYGENCONTAINING GAS, HAVING A SUBSTANTIAL DIFFERENCE BETWEEN ACID AND SAPONIFICATION VALUE, AND FURTHER CHARACTERIZED BY CONTAINING, AS COMPONENTS OF THE PORTION ACCOUNTING FOR THE DIFFERENCE BETWEEN ACID AND SAPONIFICATION VALUE, COMPOUNDS CONTAINING SAPONIFIABLE GROUPS THAT ARE NOT READILY COMBINABLE WITH AN ALCOHOL UPON TREATMENT OF SAID OXIDIZED HYDROCARBON MIXTURE WITH AN ALCOHOL UNDER ESTERIFYING CONDITIONS, WHICH COMPRISES REACTING SAID OXIDIZED HYDROCARBON MIXTURE WITH AN ALCOHOL UNDER ESTERIFYING CONDITIONS TO PROVIDE AN ESTERIFIED MIXTURE CONTAINING A SUBSTANTIAL PORTION OF SAPONIFIABLE COMPOUNDS WHOSE SAPONIFIABLE GROUPS ARE ESTERIFIED WITH THE ALCOHOL AND COMPOUNDS POSSESSING SAPONIFIABLE GROUPS THAT ARE NOT COMBINABLE WITH AN ALCONOL UNDER THE ESTERIFICATION CONDITIONS, AND ADDING AN ALKALI TO THE AFORESAID ESTERIFIED MIXTURE IN AN AMOUNT AT LEAST SUBSTANTIALLY AQUIVALENT TO THE NUMBER OF SAPONIFIABLE GROUPS IN SAID ESTERIFIED MIXTURE THAT ARE NOT COMBINED WITH AN ALCOHOL BUT SUBSTANTIALLY LESS THAN AN AMOUNT OF ALKALI EQUIVALENT TO THE TOTAL NUMBER OF SAPONIFIABLE GROUPS IN SAID ESTERIFIED MIXTURE TO SELECTIVELY SAPONIFY THE COMPOUNDS IN SAID ESTERIFIED MIXTURE THAT POSSESS SAPONIFIABLE GROUPS THAT WERE NOT COMBINED WITH AN ALCOHOL, SAID ALKALI ADDITION BEING MADE IN A CONTROLLED MANNER WHEREBY, UNTIL AN AMOUNT OF ALKALI SUBSTANTIALLY EQUIVALENT TO THE NUMBER OF SAPONIFIABLE GROUPS THAT ARE NOT COMBINED WITH AN ALCOHOL HAS BEEN ADDED, THE ALKALI IN THE ESTERIFIED MIXTURE IS MAINTAINED AT A COCENTRATION LESS THAN SUFFICIENT TO LIBERATE A SUBSTANTIAL AMOUNT OF ALCOHOL FROM SAID ESTERIFIED MIXTURE. 